1. Field of the Invention
This invention relates to an organopolysiloxane composition containing a mixture of several specific types of liquid organopolysiloxanes, to emulsion-forming concentrates and aqueous emulsions formed therefrom and to the treatment of textile fiber and fabric substrates with the emulsions to improve such desirable properties of the substrates as their wettability and softness unaccompanied by any significant or appreciable yellowing.
2. Description of the Prior Art
The formulation and manufacture of organopolysiloxane-based aqueous emulsions and the treatment of natural and synthetic textile fiber and fabric substrates with the emulsions to improve one or more properties of the substrates, in particular, their softness, are well known and well developed technologies.
A major challenge in the formulation of any aqueous organopolysiloxane emulsion intended for use as a textile fiber and/or fabric treating agent is the difficulty of achieving a good, which is to say, commercially acceptable, balance in the properties of the fiber/fabric substrate treated with a given emulsion. For example, one emulsion might provide excellent softness, but at the expense of wettability and/or resistance to yellowing, another emulsion might provide excellent wettability but at the expense of softness and/or resistance to yellowing, and so forth.
Although much effort has been expended to develop aqueous organopolysiloxane emulsions that impart a good balance of properties to textile fiber and fabric substrates treated therewith, the satisfactory attainment of this goal can be quite elusive.
It is therefore an object of the invention to provide an organopolysiloxane composition which, when formulated as an aqueous emulsion and applied to a textile fiber or fabric substrate, will improve the wettability and softness properties of the substrate without, however, causing any significant or appreciable yellowing of the substrate.
Other objects of the invention include methods for making organopolysiloxane emulsion-forming concentrates and stable aqueous organopolysiloxane emulsions and employing the latter as textile treating agents.
In accordance with the present invention, an organopolysiloxane composition is provided which comprises:
a) organopolysiloxane I of the general formula 
wherein each R1 is, independently, an alkyl group of from 1 to 4 carbon atoms, R2 is a divalent hydrocarbon group, R3 is hydrogen or a monovalent hydrocarbon group, each A is, independently, an R1 group or an R2(NHCH2CH2)cNHR3 group, provided, that at least one A is an R2(NHCH2CH2)cNHR3 group, a is from 1 to about 1000, b is from 0 to about 100 and c is from 0 to about 1000;
b) organopolysiloxane II of the general formula
(AB)nA
wherein n is from 2 to about 1000, A is a polysiloxane unit of the general formula
[X(CaH2aO)bR2(Si[R1]2O)cR2(OCaH2a)bX],
B is a polyalkyleneoxide unit of the general formula [YO(CaH2aO)dY], each R1 is, independently, an alkyl group of from 1 to 4 carbon atoms, R2 is a divalent organic group, X and Y are divalent organic groups selected from a secondary or tertiary amine and a ring-opened epoxide such that when X is a ring-opened epoxide, Y is a secondary or tertiary amine and when X is a secondary or tertiary amine, Y is a ring-opened epoxide, each a is, independently, from 2 to 4, each b is independently from 0 to about 100, c is from 1 to about 500, d is from 0 to about 100 and the sum of b and d is from 1 to about 100;
c) organopolysiloxane III of the general formula
A(Si[R1]2O)x(Si[R1][E]O)y(Si[R1][G]O)zSi(R1)2A
wherein each R1 is, independently, an alkyl group of from 1 to 4 carbon atoms, E is a monovalent organic group containing at least one epoxy group, G is an xe2x80x94(R2)bO(C2H4O)c(C3H6O)dR3 group in which R2 is a divalent organic group, R3 is hydrogen or a monovalent hydrocarbon group, acyl group or monoester carbonate group, b is 0 or 1, c is from 0 to about 50, d is from 0 to about 50 and the sum of c and d is from 1 to about 100, each A is, independently, an R1 or E group, x is from 0 to about 2000, y is from 0 to about 2000, z is from 1 to about 100 and the sum of x and y is from 1 to about 2000; and,
d) organopolysiloxane IV of the general formula
A(Si[R1]2O)x(Si[R1][G])ySi(R1)2A
wherein each R1 is, independently, an alkyl group of from 1 to 4 carbon atoms, G is an xe2x80x94(R2)bO(C2H4O)c(C3H6O)dR3 group in which R2 is a divalent organic group, R3 is hydrogen, a monovalent hydrocarbon group, an acyl group or a monoester carbonate group, b is 0 or 1, c is from 0 to about 50, d is from 0 to about 50 and the sum of c and d is from 1 to about 100, each A is, independently, an R1 group or a monovalent organic group containing at least one epoxy group; x is from 0 to about 2000, y is from 0 to about 2000, and the sum of x and y is from 1 to about 2000.
Aqueous emulsions formed from the foregoing organopolysiloxane composition when applied in accordance with known and conventional methods to natural or synthetic textile fiber and fabric substrates, provide excellent levels of softness and wettability to the substrates but without discernable or apparent yellowing.
1. The Components of the Organopolysiloxane Composition
As indicated above, the organopolysiloxane composition of this invention contains individual organopolysiloxanes I-IV as hereinafter further described.
Organopolysiloxane I
Organopolysiloxane I possesses the general formula 
wherein each R1 is, independently, an alkyl group of from 1 to 4 carbon atoms, R2 is a divalent hydrocarbon group, R3 is hydrogen or a monovalent hydrocarbon group, each A is, independently, an R1 group or an R2(NHCH2CH2)cNHR3 group, provided, that at least one A is an R2(NHCH2CH2)cNHR3 group, a is from 1 to about 1000, b is from 0 to about 100 and c is from 0 to about 10.
In organopolysiloxane I, each R1 is preferably a methyl group, R2 is preferably a straight or branched chain alkylene group of from 2 to about 10 carbon atoms, ethylene and propylene being especially preferred, R3 is preferably an alkyl group of from 1 to about 10 carbon atoms, methyl being especially preferred, a is preferably from about 50 to about 700, b is preferably from about 1 to about 30, c is preferably from 1 to 4 and the sum of a and b is preferably from about 50 to about 730.
For further details concerning organopolysiloxane I, reference may be made to U.S. Pat. No. 4,459,382, the contents of which are incorporated by reference herein. Organopolysiloxane I is advantageously present in the emulsion-forming concentrate at a level of from about 1 to about 50, and preferably from about 5 to about 20, weight percent based on the total weight of organopolysiloxanes I-IV.
Organopolysiloxanes II
Organopolysiloxane II possesses the general formula
(AB)nA
wherein n is from 2 to about 1000, A is a polysiloxane unit of the general formula
[X(CaH2aO)bR2(Si[R1]2O)cR2(OCaH2a)bX],
B is a polyalkyleneoxide unit of the general formula [YO(CaH2aO)dY], each R1 is, independently, an alkyl group of from 1 to 4 carbon atoms, R2 is a divalent organic group, X and Y are divalent organic groups selected from a secondary or tertiary amine and a ring-opened epoxide such that when X is a ring-opened epoxide, Y is a secondary or tertiary amine and when X is a secondary or tertiary amine, Y is a ring-opened epoxide, each a is, independently, from 2 to 4, each b is independently from 0 to about 100, c is from 1 to about 500, d is from 0 to about 100 and the sum of b and d is from 1 to about 100.
In organopolysiloxane II, n is preferably from about 1 to about 10, each R1 is preferably a methyl group, R2 is preferably an ethylene or propylene group, each a is preferably 2 or 3, each b is preferably from 1 to about 50, c is preferably from about 10 to about 100, d is preferably from 1 to about 50, the sum of b and d is preferably from about 10 to about 50, when a ring-opened epoxide, X or Y, as the case may be, is preferably a xe2x80x94CH2CH(OH)(CH2)vCH(OH)CH2xe2x80x94, xe2x80x94CH[CH2OH](CH2)vCH(CH2OH)xe2x80x94, xe2x80x94CH2CH(OH)(CH2)vCH[CH2OH]xe2x80x94, xe2x80x94(CH2)vOCH2CH(OH)CH2xe2x80x94 or xe2x80x94(CH2)vOCH2CH(CH2[OH])xe2x80x94 group in which v is from 2 to about 6, or a ring-opened epoxide derived from xcfx89-(3,4-epoxycyclohexyl) alkylene, xcex2-(3,4-epoxycyclohexyl) ethylene, xcex2-(3,4-epoxycyclohexyl)-xcex2-methyethylene or xcex2-(3,4-epoxy-4-methylcyclohexyl)-xcex2-methyethylene, and when a secondary or tertiary amine, X or Y, as the case may be, is preferably of the type xe2x80x94R4N(R3)(R4)gxe2x80x94 in which R3 is hydrogen or an alkyl group of from 1 to 4 carbon atoms, methyl being especially preferred, and R4 is and alkylene, cycloaliphatic alkylene or aralkylene group, which may include heteroatom(s), an alkylene of less than 10 carbons being especially preferred, and g is 0 or 1.
It is preferred that the amine functionality in organopolysiloxane II be present in the terminal A group of the (AB)n A polymer. The polyoxyalkylene blocks represented by (CaH2aO) or (OCaH2a) may be derived from one or more of the following alkylene oxides: ethylene oxide (a=2), propylene oxide (a=3) and butylene oxide (a=4). The ratios among mixtures of such oxides is not of particular importance but may be adjusted as required for the desired solubility parameters of the resulting copolymer.
For further details concerning organopolysiloxane II, reference may be made to U.S. Pat. No. 5,807,956, the contents of which are incorporated by reference herein. Organopolysiloxane II is advantageously present in the emulsion-forming concentrate at a level of from 1 to about 80, and preferably from about 10 to about 50, weight percent based on the total weight of polyorganosiloxanes I-IV.
Organopolysiloxane III
c) Organopolysiloxane III possesses the general formula
A(Si[R1]2O)x(Si[R1][E]O)y(Si[R1][G]O)zSi(R1)2A
wherein each R1 is, independently, an alkyl group of from 1 to 4 carbon atoms, E is a monovalent organic group containing at least one epoxy group, G is an xe2x80x94(R2)bO(C2H4O)c(C3H6O)d R3 group in which R2 is a divalent organic group, R3 is hydrogen or a monovalent hydrocarbon group, acyl group or monoester carbonate group, b is 0 or 1, c is from 0 to about 50, d is from 0 to about 50 and the sum of c and d is from 1 to about 100, each A is, independently, an R1 or E group, x is from 0 to about 2000, y is from 0 to about 2000, z is from 1 to about 100 and the sum of x and y is from 1 to about 2000.
In organopolysiloxane III, each R1 is preferably methyl, E is preferably an epoxy-containing group of the structure 
in which R4 is a divalent substituted or unsubstituted organic group such as methylene, ethylene, propylene, phenylene, chloroethylene, flouroethylene, xe2x80x94CH2OCH2CH2CH2xe2x80x94, xe2x80x94CH2CH2OCH2CH2xe2x80x94, xe2x80x94CH2OCH2CH2(CH3)OCH2CH2xe2x80x94 or xe2x80x94CH2CH2OCH2CH2xe2x80x94, in group G, divalent organic group R2 is preferably selected from alkylene groups of from 1 to about 5 carbon atoms and groups in which a xe2x80x94C6H4xe2x80x94 group, xe2x80x94COxe2x80x94 group or xe2x80x94NHCOxe2x80x94 group is bonded to an alkylene group, R3 is preferably hydrogen, an alkyl group of from 1 to 4 carbon atoms, an acyl group of from 1 to 4 carbon atoms or a monoester carbonate group of from 1 to 4 carbon atoms in its ester moiety, b is preferably 3, c is preferably from 1 to about 35, d is preferably from 1 to about 35 and the sum of c and d is preferably from 2 to about 70, A is preferably selected from one of the aforesaid preferred R1 and preferred E groups, x is preferably from about 10 to about 1000, y is preferably from about 1 to about 50, z is preferably from 1 to about 50 and the sum of x and y is preferably from 1 to about 1100.
For further details concerning organopolysiloxane III, reference may also be made to U.S. Pat. No. 4,459,382 referred to supra. Organopolysiloxane III is advantageously present in the emulsion-forming concentrate at a level of from about 5 to about 50, and preferably from about 10 to about 30, weight percent based on the total weight of organopolysiloxanes I-IV.
Organopolysiloxane IV
Organopolysiloxane IV possesses the general formula
A(Si[R1]2O)x(Si[R1][G])ySi(R1)2A
wherein each R1 is, independently, an alkyl group of from 1 to 4 carbon atoms, G is an xe2x80x94(R2)bO(C2H4O)c(C3H6O)dR3 group in which R2 is a divalent organic group, R3 is hydrogen, a monovalent hydrocarbon group, an acyl group or a monoester carbonate group, b is 0 or 1, c is from 0 to about 50, d is from 0 to about 50 and the sum of c and d is from 1 to about 100, each A is, independently, an R1 group or a monovalent organic group containing at least one epoxy group; x is from 0 to about 2000, y is from 0 to about 2000, and the sum of x and y is from 1 to about 2000.
In organopolysiloxane IV, R1 is preferably methyl, in group G, divalent organic group R2 is preferably selected from alkylene groups of from 1 to about 5 carbon atoms and groups in which a xe2x80x94C6H4xe2x80x94 group, xe2x80x94COxe2x80x94 group or xe2x80x94NHCOxe2x80x94 group is bonded to an alkylene group, R3 is preferably hydrogen, an alkyl group of from 1 to 4 carbon atoms, an aryl group of from 1 to 4 carbon atoms or a monoester carbonate group of from 1 to 4 carbon atoms in the ester moiety, b is preferably 3, c is preferably from 1 to about 35, d is preferably from 1 to about 35 and the sum of c and d is preferably from 2 to about 70, A is preferably selected from methyl and an epoxy-containing group E of the structure 
in which R4 is a divalent substituted or unsubstituted organic group such as methylene, ethylene, propylene, phenylene, chloroethylene, flouroethylene, xe2x80x94CH2OCH2CH2CH2xe2x80x94, xe2x80x94CH2CH2OCH2CH2xe2x80x94, xe2x80x94CH2OCH2CH2(CH3)OCH2CH2xe2x80x94 or xe2x80x94CH2CH2OCH2CH2xe2x80x94, x is preferably from about 10 to about 1000, y is preferably from 1 to about 100 and the sum of x and y is preferably from about 10 to about 1100.
For further details concerning organopolysiloxane IV, reference may again be made to U.S. Pat. No. 4,459,382. Organopolysiloxane IV is advantageously present in the emulsion-forming concentrate at a level of from about 5 to about 50, and preferably from about 10 to about 30, weight percent based on the total weight of organopolysiloxanes I-IV.
2 Concentrates and Aqueous Emulsions of the Organopolysiloxane Composition
The organopolysiloxane composition of this invention is especially adapted to be initially formulated either as an emulsion-forming concentrate from which a stable aqueous emulsion can be readily and conveniently prepared, or if desired, as a finished or semi-finished stable aqueous emulsion. The emulsifiers (surface active agents) that can be used in the formulation of the concentrates and finished/semi-finished aqueous emulsions can be selected from amongst any of the known and conventional emulsifiers suitable for providing stable aqueous emulsions of one or more liquid organopolysiloxanes such as organopolysiloxanes I-IV herein. Thus, for example, one or a combination of any of the following emulsifiers can be employed: nonionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, sorbitan fatty acid esters, glycerine fatty acid esters, and the like, anionic surface active agents such as sodium lauryl sulfate, sodium dodecylbenzene solfonate, sodium polyoxyethylene ether carboxylate, and the like, and cationic surface active agents such as quaternary ammonium salts, and the like. It is preferable that at least 50 percent by weight of the total amount of emulsifying agent employed is a nonionic surface active agent or a combination of nonionic surface active agents of which the overall hydrophilic lipophilic balance (HLB) value is from about 8 to about 14.
The amount of emulsifier(s) is not critical and can vary widely provided, of course, that at least an amount of emulsifier(s) is utilized, together with any optional co-emulsifier(s), that will provide a stable emulsion upon addition of water to the organo-polysiloxane composition. In general, the total amount of emulsifier utilized can vary from about 5 to about 100, and preferably from about 10 to about 50, parts by weight per 100 parts by weight of the total quantity of polyorganosiloxanes.
It is also within the scope of the invention to employ an optional co-emulsifier in the preparation of the emulsion-forming concentrate and aqueous emulsions of this invention. Co-emulsifiers that are especially advantageous for use herein include alkoxytriglycols such as methoxytriglycol, ethoxytriglycol, propoxytriglycol, butoxytriglycol, and the like, and polyalkylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol monomethyl ether, dibutylene glycol dimethyl ether, and the like. These and other co-emulsifiers, when present, can generally constitute from about 5 to about 70, and preferably from about 10 to about 50, weight percent of the combined weight of emulsifier(s) and co-emulsifier(s).
Other materials typically employed in the treatment of textile fiber and fabric substrates can be incorporated in the concentrate/emulsion of this invention in the usual amounts. Such materials include durable press resins, curing catalysts, preservatives, biocides, water soluble pigments or dyes, fragrances, fillers, pH adjustors, antifoamers, defoamers, and the like. However, it is preferable that the use of organotitanates, organozirconates, organogermanates and similar organometallic compounds be avoided since they may be irritating, corrosive to equipment or reduce the stability of the emulsions.
Aqueous emulsion-forming concentrates of the mixture of organopolysiloxanes I-IV in accordance with the present invention can be prepared by high shear mixing or agitation of a mixture of the desired polysiloxanes and suitable emulsifiers (surface active agents), optional co-emulsifiers and other optional ingredients as is well known in the art. Thus, the concentrates can be prepared by mixing with a suitable stirrer such as a homomixer or homogenizer. The organopolysiloxanes, emulsifier(s)/optional co-emulsifier(s) and other optional components in the desired amounts with or without an emulsion-forming amount of water (the former when the direct production of a finished or semi-finished emulsion is desired, the latter when a concentrate is desired) are introduced into a suitably equipped vessel. The length of time the mixture is mixed/agitated depends on the balance of the polarity between, or the hydrophilicity of, the selected organopolysiloxanes and the emulsifier(s) and optional co-emulsifier(s). The concentrate and emulsions formed therefrom exhibit excellent stability during storage, when diluted and when subjected to mechanical shearing.
The amounts of water utilized to provide an aqueous emulsion are not critical and can vary considerably depending on the nature and amounts of the components constituting a particular organopolysiloxane composition. In general, an amount of water should be utilized which results in an oil-in-water or water-in-oil type aqueous emulsion of good stability (i.e., no apparent phase separation), e.g., stability for at least about 1, and preferably at least about 7, days following storage at 55xc2x0 C. Amounts of water in most cases can range from about 20 to about 2000 parts, and preferably from about 100 to about 500, parts by weight per 100 parts by weight of the total amount of organopolysiloxanes. It may be economically beneficial to prepare an emulsion with a high organopolysiloxane content, i.e., a semi-finished emulsion, in order to reduce shipping and/or handling costs and thereafter to dilute the emulsion on site with additional water to application strength prior to use.
The aqueous organopolysiloxane emulsion of this invention can be applied to a textile fiber or fabric substrate by such known and conventional techniques as spraying, dipping, padding, kiss roll, and the like. Such operations can be followed by the removal of excess liquid employing any suitable means, e.g., a mangle, centrifugal separator, and the like, to control the amount of liquid taken up by the substrate followed by drying the treated substrate with or without the application of heat. When drying is accomplished by heating the substrate, the temperature can usually range from about 70xc2x0 to about 180xc2x0 C. for from about 1 to about 30 minutes. The amount of the aqueous emulsion applied to the textile fiber or fabric substrate will generally be such as to deposit from about 0.1 to about 5 percent by weight of combined organopolysiloxanes by weight of substrate.
The aqueous organopolysiloxane emulsions of the present invention can be used for the finishing treatment of many kinds of textile fiber and fabric substrates including polyester, acrylic, nylon, aramid and the like, as well as various types of natural fibers such as cotton, silk, wool, and the like. The forms of the substrates are not limited and include filaments, rovings, threads, woven and non-woven fabrics, knit cloths, and the like. The emulsions can also be applied to inorganic fibers such as glass fibers, carbon fibers, and the like.